Fluorine-containing linear polyesters

ABSTRACT

THIS SPECIFICATION DISCLOSED AROMATIC POLYESTERS PREPARED FROM A DICARBOXYLIC ACID REACTANT COMPRISED OF AT LEAST 20 MOL PERCENT OF 4,4&#39;&#39;-DICHLOROCARBONYLDIPHENYLSULFONE AND AN AROMATIC DIHYDROXY REACTANT CONTAINING A FLUORINE-SUBSTITUTED BISPHENOL. THE POLYESTERS HAVE HIGH MELT AND DECOMPOSITION TEMPERATURES WHICH MAKE THEM PARTICULARLY USEFUL AS HIGH TEMPERATURE COATINGS, FILMS, AND MOLDED ARTICLES.

United States Patent 3,573,250 FLUORINE-CONTAINING LINEAR POLYESTERS Edward W. Pietrusza, Morristown, and Jack R. Pedersen,

Parsippany, N.J., assignors to Allied Chemical Corporation, New York, N.Y.

N0 Drawing. Continuation-impart of application Ser. No. 641,129, May 25, 1967. This application May 6, 1968, Ser. No. 727,016

Int. Cl. C08g 17/00, 39/00 US. Cl. 26040 14 Claims ABSTRACT OF THE DISCLOSURE This specification discloses aromatic polyesters prepared from a dicarboxylic acid reactant comprised of at least 20- mol percent of 4,4-dichlorocarbonyldiphenylsulfone and an aromatic dihydroxy reactant containing a fluorine-substituted bisphenol. The polyesters have high melt and decomposition temperatures which make them particularly useful as high temperature coatings, films, and molded articles.

FLUORINE-CONTAINING AROMATIC POLYESTERS This application is a continuation-in-part of our copending application Ser. No. 641,129 filed May 25, 1967.

Aromatic polyesters and copolyesters derived from 4,4- dichlorocarbonyldiphenylsulfone and an aromatic dihydroxy component wherein the hydroxy radicals are directly attached to a ring carbon atom have high melting points and high glass transition temperatures and form thermally resistant films, fibers and molded articles.

We have now discovered that aromatic polyesters and copolyesters derived from a dicarboxylic acid component which contains at least about 20 mol percent of 4,4'-dichlorocarbonyldiphenylsulfone and a fluorine-containing bisphenol component wherein the hydroxy radicals are directly attached to a ring carbon atom have surprisingly high melt and decomposition temperatures and high glass transition temperatures and can be formed into films and molded articles, used as high temperature coatings and the like. Various reinforcing agents can be added to the polyesters of the invention for particular high temperature applications. For example, glass fiber reinforced polyesters of the invention retain their excellent tensile properties at very high temperatures, e.g. about 200 C. and higher.

The fluorine-containing bisphenols suitable in the present invention have the formula R11 R1 Rn l Q-eQ 2,2-bis(4-hydroxyphenyl) -1,1,3,3-tetrafluoropropane,

2,2-bis(4-hydroxyphenyl)hexafluoropropane,

2,2-bis(4-hydroxyphenyl) -1,1,3,3-tetrafluoro-1,3-dichloropropane,

"ice

2,2-bis(4-hydroxyphenyl)-1,1,1,3,3-pentafluoro-3- chloropropane,

2,2-bis(4-hydroxyphenyl)-1,1,1,3,3-pentafiuoropropane,

2,2-bis (4-hydroxyphenyl) perfluorobutane,

3,3-bis(4-hydroxyphenyl)perfluoropentane,

2,2-bis (4-hydroxy-3-methylphenyl hexafluoropropane,

2,2-bis(4-hydroxy-3-bromophenyl)hexafluoropropane,

2,2-bis (4-hydroxy-3-chlorophenyl hexafluoro propane,

2,2-bis 4-hydroxy-3-t-butylphenyl) 1, l-bis (4-hydroxyphenyl) l-trifluoromethyll-phenylmethane,

1, l-bis (4-hydroxyphenyl -2,2,2-trifluoroethane and the like. Mixtures of fluorine-containing bisphenols can also be employed.

In addition, other aromatic dihydroxy compounds can be substituted in part for the fluorine-substituted bisphenols described above such as l,2-, 1,3- and 1,4-dihydroxybenzene, bis (4-hydroxyphenyl dimethylmethane, 1,4-bis(p hydroxycumyl)benzene, 4,4 bis(hydroxyphenyl)sulfone and the like. Alternatively, an aliphatic dihydroxy compound can be substituted in part for the fluorine-substituted bisphenols such as a polymethylene glycol having from 2 to 10 carbon atoms, including ethylene glycol, 1,5-pentanediol, 1,10-decanediol and other glycols of this series, branched chain glycols such as 2,2- dimethyl-1,3-propanediol and the like, cyclic glycols such as l,4-di(hydroxyethyl)-benzene and any of these glycols bearing one or more inert substituents thereon. In order to retain the high temperature properties of the fluorinecontaining polyesters of the invention, no more than about mol percent of the fluorine-substituted bisphenol component should be replaced by other aromatic or aliphatic dihydroxy compounds.

Copolyesters can also be prepared by substituting other aromatic or aliphatic dicarboxylic acids, or their halide, ester or anhydride derivatives, for the 4,4-dichlorocarbonyldiphenylsulfone reactant in amounts of up to about 80 mol percent of the dicarboxylic acid component.

Suitable aromatic dicarboxylic acids useful for this purpose include for example phthalic acid, terephthalic acid, isophthalic acid, 4,4-diphenylmethanedicarboxylic acid, 2,2-(4,4-dicarboxydiphenyl)propane, and the like. Aliphatic dicarboxylic acids suitable in the invention include oxalic acid, adipic acid, sebacic acid, oc,a-Clithyl adipic acid, dodecanedioic acid and the like.

The polymers of the invention are prepared by reacting 4,4-dichlorocarbonyldiphenylsulfone, alone or in admixture with a different dicarboxylic acid as hereinabove described, with an equimolar amount of a fluorine-substituted bisphenol, alone or in admixture with another dihydroxy compound, in a catalyzed solution. The mixture is reacted until evolution of hydrogen chloride has ceased. By varying the conditions of time and temperature and concentrations of starting materials, a wide range of fluorine-containing sulfone polyesters and copolyesters can be prepared of determinable molecular Weight.

Equimolar amounts of the 4,4'-dichlorocarbonyldiphenylsulfone reactant and the dihydroxy reactant are preferred in our process since the presence of an excess of either reactant Will act as a terminator for the polymerization reaction resulting in the formation of low molecular weight polyesters.

The solvent should be a solvent for both the 4,4'-dicholorcarbonyldiphenylsulfone reactant and the dihydroxy reactant and preferably for the resultant polyester, although this is not required. In general, aromatic hydrocarbons and halogenated aromatic hydrocarbons are solvents which may be employed in the process of the invention, including benzene, toluene, o-xylene, m-xylene, p-xylene, p-cymene, diphenylmethane, 1,3,5-triethylbenzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, and the like. In general, the use of higher boil- 3 4 ing solvents will result in the formation of higher molecu- 1,3-dichloropropane, 2.5 X 10- part of powdered magnelar weight polymers. sium and 220 parts by volume of freshly distilled o-di- 1 Thi reaitants can be lfaeated in1 the albsence of a cattfirchlgrobenzene were chargeid to 11. reactign vesseTlh fitted yst ut t e presence 8. meta cata yst increases e wit a magnetic stlrrer an a re uX con enser. e rerate of reaction. Particularly outstanding results were 5 action mixture was refluxed until the evolution of hydroobtained using powdered magnesium a; the galtalyst. h gen lchloride ceased, abgilt 50i htgurs, and? nitrogimt. The

The p0 ymerization reaction procee s rea iy at t e resu tant mixture was tere roug gass W00 0 rereflux temperature of the reaction mixture which depends move the catalyst and the solution poured into 500 parts upon the boiling point of the solvent employed during by volume of methanol. polymerization. In general, the rate of polymerization A white polymer product was isolated and dried. The will increase at higher temperatures of reaction. polymer had a flow point range of 250-260 C., a reduced The time required for the formation of high molecular viscosity of 0.15 and T of 190 C. The polymer did not weight polyester will vary depending upon the temperadecompose up to 300 C. ture of the reaction, the purity of the reactants and the The polymer has recurring units of the formula (H) CFzCl choice of catalysts. The reactants and the solvent must EXAMPLE 2 be essentially free from 1mpur1t1es and water whlch cause 1715 parts of 4, 4, dich10rocarbonyldiphenylsulfone, degradative side reactions and chaln termination and pre- 15 4 parts of 2,2-bis(4-hydroxyphenyl) 1,1 trifluorovent the formation of high molecular weight polymer. Inethane, OJ part of powdered magnesium and 400 parts creasing the time of reaction increases the molecular by volume of odichlorobenzene were refluxed for 48 Weight the f Polymer with accompanying 2 hours in a vessel as in Example 1. The mixture was filcreases in glass transition temperature, flow temperature, tered and the polymer product precipitated, isolated and and decompositiontemperature. dried as in Example 1,

The polymer product can be isolated in any convenient Th Polymer d t h d flow point range of 285; manner such as will be known to one skilled in the art. 295 C., a reduced viscosity of 0.41 and a T of 225 C. One convenient method is to filter 01f the catalyst and 3 The polymer has recurring units of the formula 0 o 0 CF u i n n 3 --o fioo (|3 opour the reaction mixture into a nonsolvent for the poly- EXAMPLE 3 he Precipitated Polymer can be further Purified by 17.15 parts of 4,4'-dichlorocarbonyldiphenylsulfone, washmg and drymg to remove Solvent h 40 17.2 parts of 1,l-bis(4-hydroxyphenyl)-l-trifluorometh l- The polyesiters and copolyestersrof e z g l-phenylmethane, 0.1 part of powdered magnesium and useful P hlgh temperature i canons 400 parts by volume of o-dichlorobenzene were refluxed fprmed Into molqqd amc es and the for 18 hours in a vessel as in Example 1. The solution was l composltes compnsmg the Rolyfisters O the mven' filtered and the product isolated and dried as in Extion and up to about 99% by weight of the polymer of ample 1.

. a remforgmg agept cap be preqared gg 22.5 parts of polymer were obtained having a flow means. Suitable relnforcing agents include g ass ers an point of 3404500 C a reduced viscosity of 0.45 and a glass cloth, metal fibers, metal carbide whiskers and the Tg of C.

Z F amces be g g g the gf gg The results of thermogravimetrie analysis at various gg g zg g g gfi fi i g gg agerft y Welg 0 5O temperatures in nitrogen and in air, expressed as percent The following examples are given to further illustrate Welght loss are glvm below the invention, but it is to be understood that the invention Atmosphere 400 C. Q 5000 Q 5500 C. is not meant to be limited to the details disclosed therein.

the examples all P r r by Weight mess other- $595312:::::::::::::::::: 3:3 81% 3:3 3%:3 wise noted. The reduced vlscosrty of the polymers was determined as 3. 0.52% by weight solution in m-cresol at Th pglymer roduct has recurring units of the 25 C. Glass transition temperatures, referred to as T,;, formula 0 O 0 CF;

and decomposition temperatures were determined by dif- A 10% solution of the polymer in o-dichlorobenzene ferential thermal analysis except when otherwise noted. was prepared and divided into three portions. One por- The tensile property measurements reported were car tion was reserved, a small amount of oil of orange was ried out using an Instron tensile tester operated at a conadded to the second portion and a small amount of tistant speed crosshead separation of 0.5 inch per minute. tanium dioxide was added to the third portion. Three EXAMPLE 1 films were cast from the solutions by pouring onto a glass plate and evaporating the solvent. A clear film was ob- 3.429 parts of 4,4'-dichlorocarbonyldlphenylsulfone, tained from the first solution, an orange film from the 3.0 parts of 2,2-bis(4-hydroxyphenyl)1,1,3,3-tetrafluorosecond, and a white film from the third solution.

The tensile properties of a clear cast film prepared as above were determined at room temperature and at an elevated temperature. The results are given below:

Ultimate Ultimate elongation, tensile 2% secant Temperature, 0. percent strength, p.s.i. modulus, p.s.i.

EXAMPLE 4 A portion of the second polymer was dissolved in odichlorobenzene and a film was cast on a glass plate. The film had the following tensile properties:

Ultimate Ultimate 2% secant elongation, tensile strength, modulus,

Temperature, C. percent p.s.i. p.s.i'

EXAMPLE 6 34.3 parts of 4,4'-dichlorocarbonyldiphenylsulfone, 20.3 parts of isophthaloyl chloride, 67.2 parts of 2,2-bis(4-hydroxyphenyl)perfluoropropane, 0.4 part of powdered magnesium and 800 parts by volume of o-dichlorobenzene were refluxed for hours. The copolymer product was isolated and dried following the procedure of Example 1.

The copolymer had a reduced viscosity of 0.52, a melt flow of 290310 C. and a T of 220 C.

A brittle, opaque film was cast from a solution of the polymer in o-dichlorobenzene.

Thermogravimetric analysis of the polymer was made under a nitrogen atmosphere and in air. The percent Weight loss at various temperatures is given below:

Atmosphere 400 0. 450 C. 500 0. 550 C.

Nitrogen 0 0. 5 7. 0 38. 0 Air 0 1. 5 10. 5 43. 0

Comparison toan analogous polymer prepared from 4,4 dichlorocarbonyldiphenylsulfone and 2,2 bis(4-hydroxyphenyl) propane demonstrates that the fluorine-containing polymer has a higher resistance to elevated temperatures. The thermogravimetric analysis results from the nonfiuorine-containing polymer are given below:

34.3 parts of 4,4'-dichlorocarbonyldiphenylsulfone, 16.8 parts of 2,2-bis(4-hydroxyphenyl)perfluoropropane, 17.2 parts of 1,1 bis(4-hydroxyphenyl) 1 trifluoromethyl-lphenylmethane, 0.2 part of powdered magnesium and 650 parts by volume of o-dichlorobenzene were charged to a vessel as in Example 1 and refluxed for 24 hours. A small portion of the mixture was taken off and the remainder refluxed for 24 hours longer. The catalyst was filtered and the polymer products isolated and dried.

The first sample had a reduced viscosity of 0.25 and a T of 220 C.

The second sample had a higher reduced viscosity of 0.46, a melt flow of 325-340 C. and a T of 255 C.

The results of thermogravimetric analysis on the second copolymer expressed as percent weight loss at various temperatures is given below:

A film was cast from a solution in o-dichlorobenzene. Tensile properties are given below:

Ultimate Ultimate 2% secant elongation, tensile strength, modulus Temperature, 0. percent p.s.i. p.s.i.

A sheet was compression molded from the above polymer and tensile properties determined. The results are given below:

Ultimate Ultimate 2% secant elongation, tensile strength, modulus, Temperature, C. percent p.s.i. p.s.i.

Test specimens of the molded sheet were heated for 43 hours in an air oven at 200 C. and cooled to room temperature. The ultimate elongation was 10%, ultimate tensile strength 16,000 p.s.i. and 2% secant modulus 214,300 p.s.i.

39 parts of the copolymer prepared above were dissolved in 200 parts by volume of o-dichlorobenzene. Various amounts of A" glass fibers which had been previously washed with hot methanol and hot o-dichlorobenzene were added. The polymer was isolated and dried as in Example 1.

Samples of the glass reinforced copolymer were compression molded at 315 C. and tensile properties determined. The results are summarized below:

It will be apparent that numerous variations and modifications may be eflected without departing from the novel concepts of the present invention, and the illustrative details disclosed are not to be construed as imposing undue limitations on the invention.

We claim:

1. A fluorine-containing aromatic film forming polyester consisting essentially of a condensation reaction product of equimolar amounts of (A) a dicarboxylic acid reactant comprising from 100 to about 20 mol percent of 4,4-dichlorocarbonyldiphenylsulfone and from to about bonyl-diphenylsulfone contains from about '1 to about 80 mol percent of a different dicarboxylic acid reactant.

4. A polyester according to claim 1 wherein said dicarboxylic acid reactant in addition to 4,4-dichlorocarbonyldiphenylsulfone contains from about 1 to about 80 mol percent of an aromatic dicarboxylic acid reactant.

5. A polyester according to claim 4 wherein said aromatic dicarboxylic acid reactant is isophthaloyl chloride.

6. A linear aromatic film forming polyester consisting essentially of units of the formula 80 mol percent of a different dicarboxylic acid reactant wherein R and R are independently selected from the with (B) a bisphenol reactant containing fluorine comprising from 100 to about 20 mol percent of one or more fluorine-containing bisphenols of the formula wherein R and R are independently selected from the group consisting of hydrogen, phenyl and fluoroalkyl radicals of 1 to 5 carbon atoms wherein at least two fluorine atoms are attached to each carbon atom and the remaining substituents can be hydrogen, fluorine or chlogroup consisting of hydrogen, phenyl and fluoroalkyl radicals of 1 to 5 carbon atoms wherein at least two fluorine atoms are attached to each carbon atom and the remaining substituents can be hydrogen, fluorine or chlorine,

and wherein at least one of the groups R and R contains 8. A film forming polyester consisting essentially of units of the formula rine; and wherein at least one of the groups R and R contains fluorine; R at each occurrence is a substituent 9. A film forming polyester consisting essentially of units of the formula selected from the group consisting of halogen and alkyl radicals of 1 to 5 carbon atoms; and n is an integer from 10. A film forming polyester consisting essentially of units of the formula 0 to 4, and from 0 to 80 mol percent of a different dihydroxy compound.

2. A polyester according to claim 1 phenol reactant comprises a mixture of two or more fluorine-containing bisphenols as described.

3. A polyester according to claim 1 wherein said di- 11. A film formed from the polyester of claim 1. 12. A composite formed from polyester of claim 1 wherein Said containing from about 1 to about 99% by weight of the polyester of a reinforcing agent selected from the groups consisting of glass fibers, glass cloth, metal fibers and metal carbide whiskers.

13. A mold article formed from the polyester of claim carboxylic acid reactant in addition to 4,4-dichlorocar- 1 containing from 1 to about by weight of the polyester of a reinforcing agent selected from the group con- OTHER REFERENCES sisting of glass fibers, glass cloth, metal fibers and metal vinogradova et ah DokL Akad Nauk SSSR 164 Carblde whlskers- 563-6 (1965) (Chem. Abstr. supplied).

14. molded artlcl e accordlng to clalm 13 whereln Korshak et ah Akad Nauk SSSR Ser. Khim sald relnforclng agent 1s glass fibers. 5 1965, 1649 54 (C. Supplied).

Reference Cited Korshak et aL: Vysokomolecul. Soedin. 7, 1689-92 s (1965) c. A. supplied). UNITED STATES PATENTS 3,028,364 4/1962 Conix et a1. 260-47 WILLIAM SHORT, Primary Examiner 3,297,633 1/1967 Hindersinn et a1 26047 10 LD TEIN Assistant Examiner FOREIGN PATENTS U'IS. CL X R- 132,403 10/1960 Russia. 26049 

